CN115915875B - Preparation method of full-slit coated large-area perovskite solar cell - Google Patents
Preparation method of full-slit coated large-area perovskite solar cell Download PDFInfo
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- CN115915875B CN115915875B CN202210480076.3A CN202210480076A CN115915875B CN 115915875 B CN115915875 B CN 115915875B CN 202210480076 A CN202210480076 A CN 202210480076A CN 115915875 B CN115915875 B CN 115915875B
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Abstract
The invention discloses a preparation method of a full-slit coating large-area perovskite solar cell, which belongs to the technical field of solar cells and comprises the following specific steps of: the functional layers are prepared by the substrate surface activation and vacuum assisted slit coating technology. The surface of the FTO glass substrate is activated by adopting Ultraviolet (UV) -ozone or oxygen plasma treatment, so that the coating of precursors of all functional layers is facilitated; by adopting the multistage GAP coating, a more uniform and complete film can be obtained; the vacuum assisted slot coating technique was used to build gentle vacuum within 10S to remove excess solvent from the newly deposited precursor wet film before uniform nucleation and crystallization runaway, thereby stabilizing the mesophase. The whole process adopts a slit coating technology for the main part, has low coating cost, simple process, good efficiency and stability of the device and good reproducibility.
Description
Technical Field
The invention relates to the technical field of solar cells, in particular to a preparation method of a large-area perovskite solar cell.
Background
Perovskite Solar Cells (PSCs) are a representative of third generation photovoltaic solar cells, which have been attracting attention due to their unique characteristics of light weight, strong flexibility, low cost, low temperature dissolution process, etc., and for decades, their authentication efficiency has been as high as 25.7%, and perovskite/Si stacked devices manufactured by the berlin helmholtz center have achieved 29.8% authentication efficiency, breaking through 30% of the dactylotheca.
Crystalline silicon (c-Si) solar cells currently have a share of more than 90% of the global photovoltaic market and their authenticated Power Conversion Efficiency (PCE) reaches 26.7%, approaching the theoretical limit. The focus of photovoltaic development is therefore to further increase efficiency with minimal additional cost, and it is therefore important to design novel and efficient photovoltaic devices.
In order to introduce PSCs technology into the market that has been dominated by silicon solar cells for decades, there are many challenges to overcome, two factors such as large area module fabrication and operational stability often show an inverse dependence. In the conventional spin coating process, the thickness of the center and the edge of the substrate is different due to non-uniformity of centrifugal force, especially for a large area film. Thicker areas show increased non-radiative recombination losses, thinner areas show reduced light extraction, increased pinholes, resulting in reduced efficiency. Moreover, the conventional spin coating process cannot meet the preparation requirements of the market on perovskite batteries with large area, high flux and low cost.
For cells with large area perovskite PCEs still lagging the existing small area PCEs, it has been agreed that large area thin films, especially perovskite thin films, are not only superior to the existing developments of small area cells in terms of device efficiency, but also in terms of research on failure mechanisms. To solve these problems, development of a large-area coating method is an effective method.
Disclosure of Invention
In view of the above, the invention provides a preparation method of a large-area perovskite solar cell, which overcomes the defects of low efficiency and poor stability of a large-area device in the existing spin coating technology.
In order to achieve the above object, the present invention provides the following technical solutions: a preparation method of a full-slit coated large-area perovskite solar cell comprises the following specific steps: substrate surface activation: placing the cleaned and etched FTO glass substrate into Ultraviolet (UV) -ozone treatment equipment for 15min, or treating for 3min by using oxygen plasma, so that each functional layer solution can be adsorbed better;
vacuum assisted slit coating technique to prepare functional layers: the precursor solution of each functional layer is coated on the FTO glass substrate by using a slit coating device, and the distance GAP between a coating cutter head and a substrate is set to a plurality of values, so that a uniform and complete film can be obtained; rapidly placing the wet film obtained by coating into a mild vacuum of 20Pa for vacuum extraction, carrying out illumination treatment to obtain a perovskite dry film, and carrying out annealing treatment;
the surface activation, except after the FTO substrate glass is cleaned, is subjected to surface activation, so that some organic matters are removed, and the surface of the tin dioxide film can be further treated after the tin dioxide film is coated, so that the coating of a perovskite precursor is facilitated;
preparing each functional layer by the vacuum auxiliary slit coating technology, wherein a tin dioxide film is coated on a surface-activated FTO glass substrate and is subjected to 110 ℃ annealing treatment for 40-50min; the volume ratio of tin dioxide to deionized water in the precursor solution is 1:3, a step of; the slit coating speed is 1m/min;
the thickness of a gasket of a cutter head used by the slit coating equipment is 0.01-0.05 mm; all functional layers adopt a multi-section GAP blade coating mode, and the method comprises the following steps:
when the coating length is L, the distance GAP value G=0.030-0.080 mm between the cutter head and the substrate during the period from the beginning of liquid injection to the connection of the liquid bead and the substrate to form meniscus liquid level;
GAP value was 0.9G during the period from the start of coating to the arrival of 0.2L of the coating stroke;
the GAP value is reduced from 0.9G to 0.7G during the stroke of 0.2L to 0.6L;
the GAP value is reduced from 0.7G to 0.5G during the 0.6L-L stroke;
the perovskite absorption layer is coated on the tin dioxide film subjected to the surface activation treatment, and the slit coating speed is 1.5m/min. Immediately transferring into a vacuum box after coating, cooling to a gentle vacuum of 20Pa in 10S, maintaining for 2min, simultaneously irradiating, and then annealing;
the Spiro-OMeTAD hole transport layer was coated on the perovskite absorber layer at a slit coating speed of 0.4m/min.
Compared with the prior art, the invention discloses a preparation method of a large-area perovskite solar cell, which has the following beneficial effects:
1) Preparing a film by adopting slit coating with multiple GAP values, so as to realize large-area solar cell devices and uniform film;
2) By vacuum assisted slot coating techniques, rapid evaporation of the solvent is achieved while illumination is taking place, effectively separating wet film precursor deposition from subsequent thermal annealing and crystallization at room temperature, and depositing high quality perovskite thin films in a controlled manner.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
FIG. 1 is a schematic view (front view) of a vacuum box of a vacuum assisted slot coating process according to an embodiment;
fig. 2 is a schematic view (top view) of a vacuum-assisted slot coating process vacuum box according to an embodiment.
Detailed Description
The technical solutions of the embodiments of the present invention will be described below with reference to the drawings in the embodiments of the present invention, and of course, the described embodiments are only some of the embodiments of the present invention.
The embodiment of the invention discloses a preparation method of a full-slit coated large-area perovskite solar cell, which comprises the following steps of:
the FTO glass with the size of 7CMX12CM is cleaned and dried, then is put into Ultraviolet (UV) -ozone treatment equipment for 15min, or is treated by oxygen plasma for 3min, and then is put into a slit coating glove box for use;
coating tin dioxide precursor solution on an FTO glass substrate by a slit coating device, wherein the thickness of a gasket used by a cutter head is 0.01mm, the coating speed is 1m/min, and annealing the tin dioxide film obtained by coating in air at 110 ℃ for 40-50min;
repeating the steps, coating a perovskite precursor solution on an FTO glass substrate containing a tin dioxide layer, enabling the thickness of a gasket used by a cutter head to be 0.05mm, enabling the coating speed to be 1.5m/min, then rapidly placing the gasket into a vacuum box of a vacuum auxiliary slit coating process, enabling the pressure to be reduced to 20Pa at about 10S, maintaining for one minute, and annealing the obtained perovskite film in a nitrogen glove box at 150-160 ℃ for 15-20min;
coating a Spiro-OMeTAD precursor solution on an FTO glass substrate containing a tin dioxide layer and a perovskite layer, wherein the thickness of a gasket used by a cutter head is 0.03mm, the coating speed is 0.4m/min, and then carrying out metal electrode preparation on the obtained semi-finished product of the battery to obtain the large-area solar battery.
Claims (6)
1. The preparation method of the full-slit coated large-area perovskite solar cell is characterized by comprising the following specific steps of:
substrate surface activation: placing the cleaned and etched FTO glass substrate into Ultraviolet (UV) -ozone treatment equipment for 15min, or treating for 3min by using oxygen plasma, so that the solutions of all functional layers can be adsorbed better;
preparing each functional layer comprising an electron transport layer, a perovskite film absorption layer and a hole transport layer by using a vacuum auxiliary slit coating technology, scraping precursor solution of each functional layer on an FTO glass substrate by using a slit coating device, setting a plurality of values of the distance GAP between a coating tool bit and a substrate, and finally obtaining a uniform and complete film;
the thickness of a gasket of a cutter head used by the slit coating equipment is 0.01-0.05 mm;
the slit coating equipment adopts a multistage GAP blade coating mode and comprises: when the coating length is L, the distance GAP value G=0.030-0.080 mm between the cutter head and the substrate during the period from the beginning of liquid injection to the connection of the liquid bead and the substrate to form meniscus liquid level;
GAP value was 0.9G during the period from the start of coating to the arrival of 0.2L of the coating stroke;
the GAP value is reduced from 0.9G to 0.7G during the stroke of 0.2L to 0.6L;
the GAP value is reduced from 0.7G to 0.5G during the 0.6L-L stroke;
in the step of vacuum assisted slot coating of the perovskite thin film absorber layer,
solutes of the perovskite precursor solution included lead iodide, lead chloride, cesium iodide, formamidine iodine, methylamine bromide, and methylamine chloride in a molar ratio of 1.30:0.03:0.07:0.35: 0.05-0.1: 0.08-0.1;
the perovskite precursor solution is prepared from a mixture of dimethyl sulfoxide, N-dimethylformamide and isopropanol in a volume ratio of 2:2: 1-8: 1:1, a step of;
the slit coating speed of the perovskite precursor solution is 1.5m/min;
and rapidly placing the wet film obtained by coating into a mild vacuum of 20Pa for vacuum extraction, carrying out illumination treatment to obtain a perovskite dry film, and carrying out annealing treatment.
2. The method for preparing a full-slit coated large-area perovskite solar cell according to claim 1, wherein the specific steps of the slit coating of the electron transport layer are as follows: coating a tin dioxide film on the surface-activated FTO glass substrate, and carrying out 110 ℃ annealing treatment for 40-50min;
the volume ratio of tin dioxide to deionized water in the tin dioxide film precursor solution is 1:3, a step of;
the slit coating speed of the tin dioxide film is 1m/min.
3. The method for preparing the full-slot coated large-area perovskite solar cell according to claim 2, wherein the electron transport layer slot coating further comprises the step of further treating the surface of the tin dioxide film after coating, thereby being more beneficial to the coating of perovskite precursors.
4. The method for preparing a full-slit coated large-area perovskite solar cell according to claim 1, wherein the film forming treatment by the vacuum assisted slit coating technology is completed within 30-120 s after the preparation of a perovskite thin film by using a multistage GAP process in combination with slit coating based on the precursor solution;
the vacuum box used by the vacuum auxiliary slit coating technology is cylindrical, and the bottom area of the vacuum box meets S# < S <1.25S#, wherein S# is the bottom area of the coated substrate; the height H=4dmm-7dmm of the vacuum box; wherein d represents the thickness of the substrate;
when the perovskite thin film is prepared by the vacuum auxiliary slit coating technology for film forming treatment, the illumination is the irradiation of an experimental ultraviolet lamp; the air pressure of the vacuum box is reduced to 20Pa within 10 s; the pumping speed of the vacuum pump connected with the vacuum box is more than 8L/s.
5. The method for preparing a full-slit coated large-area perovskite solar cell according to claim 1, wherein the specific step of slit coating the hole transport layer is as follows: coating a Spiro-ome tad solution on FTO glass containing the electron transport layer and the perovskite thin film absorption layer;
the volume ratio of the lithium salt, the cobalt salt and the tributyl phosphate in the Spiro-OMeTAD solution is 18:30:29;
the volume ratio of Li-TFSl to acetonitrile in the lithium salt solution is 13:25;
the volume ratio of FK209 to acetonitrile in the cobalt salt solution is 3:10;
the slot coating speed of the Spiro-OMeTAD solution was 0.4m/min.
6. A method of manufacturing a full slot coated large area perovskite solar cell as claimed in claim 3 wherein the thickness of the tin dioxide thin film is 50-70nm; the annealing treatment temperature of the perovskite dry film is 150-160 ℃, and the annealing time is 15-20min; the thickness of the perovskite film absorption layer is 600-800 nm.
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| CN109830609A (en) * | 2019-02-13 | 2019-05-31 | 南方科技大学 | A kind of large area flexible perovskite solar battery and printing preparation method |
| CN110349886A (en) * | 2019-06-19 | 2019-10-18 | 江苏大学 | Large-area perovskite solar cell preparation device and preparation method |
| WO2021040442A2 (en) * | 2019-08-30 | 2021-03-04 | 광주과학기술원 | Laser-based multiple printing apparatus and method for fabricating surface-morphology-controlled large-area perovskite thin film by using same |
| CN113457917A (en) * | 2021-06-30 | 2021-10-01 | 无锡极电光能科技有限公司 | Coating equipment and method for preparing perovskite light absorption film by using same |
| CN113871538A (en) * | 2021-10-13 | 2021-12-31 | 深圳黑晶光电技术有限公司 | Preparation method of perovskite thin film by applying vacuum flash evaporation to assist slit coating |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109830609A (en) * | 2019-02-13 | 2019-05-31 | 南方科技大学 | A kind of large area flexible perovskite solar battery and printing preparation method |
| CN110349886A (en) * | 2019-06-19 | 2019-10-18 | 江苏大学 | Large-area perovskite solar cell preparation device and preparation method |
| WO2021040442A2 (en) * | 2019-08-30 | 2021-03-04 | 광주과학기술원 | Laser-based multiple printing apparatus and method for fabricating surface-morphology-controlled large-area perovskite thin film by using same |
| CN113457917A (en) * | 2021-06-30 | 2021-10-01 | 无锡极电光能科技有限公司 | Coating equipment and method for preparing perovskite light absorption film by using same |
| CN113871538A (en) * | 2021-10-13 | 2021-12-31 | 深圳黑晶光电技术有限公司 | Preparation method of perovskite thin film by applying vacuum flash evaporation to assist slit coating |
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